CN115403081A - High-nickel ternary positive electrode material, preparation method thereof and battery - Google Patents
High-nickel ternary positive electrode material, preparation method thereof and battery Download PDFInfo
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Abstract
The invention discloses a high-nickel ternary cathode material, a preparation method thereof and a battery, and belongs to the technical field of batteries. The preparation method comprises the following steps: mixing a high-nickel ternary material primary-fired material with Zr-based UIO-66, and then carrying out high-temperature heat treatment in an oxygen atmosphere to obtain a primary coating material; mixing the primary coating material with a boron source, and carrying out low-temperature heat treatment in an oxygen atmosphere to obtain a composite coated high-nickel ternary cathode material; wherein, the high nickel ternary material is sinteredThe molecular formula of the material is LiNi x Co y Mn 1‑x‑y O 2 X is more than or equal to 0.7 and less than or equal to 1,0.0 and less than or equal to 0.3. The method can prepare the high-nickel ternary cathode material with better cycle performance and rate performance, and the corresponding material not only can prevent electrolyte permeation and surface interface side reaction, but also has a lower charge transfer resistance value and is beneficial to lithium ion transmission.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a high-nickel ternary cathode material, a preparation method thereof and a battery.
Background
The high nickel ternary anode material has high specific capacity and is gradually widely applied, but with the increase of the Ni content in the material, the interface is unstable and the structure is degraded in the charging and discharging process, and the capacity is rapidly attenuated, so that the cycle performance is poor, and the practical application of the high nickel ternary anode material is seriously limited.
On the one hand, the nickel content is increased, and in a charged state, severe contraction/expansion of the crystal lattice caused by phase transition (H2 → H3) causes severe strain to be generated inside the particles, resulting in poor structural cycle stability and thermal stability thereof. On the other hand, due to Li + Ni, a highly oxidizing species 4+ And the side reaction is easy to occur with electrolyte on the surface of the material, and the intergranular cracks are used as electrolyte permeation channels, so that the side reaction is intensified, and the structure is further deteriorated.
The doping modification relieves the phase change degradation of the high-nickel anode material body phase structure to a certain extent, but the doping modification cannot effectively solve the problem of 'surface-to-interior' structure degradation caused by serious side reaction between the surface and the electrolyte. For this reason, it is critical to coat the surface of the material with a dense, thin layer. But the coating layers of the traditional oxides such as alumina, zirconia, titania and the like are not uniform; and because the chemical inertia is not beneficial to lithium ion transmission, the specific capacity and the rate capability are reduced.
In view of this, the invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a high-nickel ternary cathode material, which can prepare the high-nickel ternary cathode material with better cycle performance and rate capability.
The second purpose of the invention is to provide a high-nickel ternary cathode material prepared by the preparation method.
The invention also aims to provide a battery prepared from the material containing the high-nickel ternary cathode material.
The application can be realized as follows:
in a first aspect, the present application provides a method for preparing a high-nickel ternary cathode material, which comprises the following steps:
mixing a high-nickel ternary material primary-fired material with Zr-based UIO-66, and then carrying out high-temperature heat treatment in an oxygen atmosphere to obtain a primary coating material;
mixing the primary coating material with a boron source, and carrying out low-temperature heat treatment in an oxygen atmosphere to obtain a composite coated high-nickel ternary cathode material;
wherein the molecular formula of the high-nickel ternary material calcined material is LiNi x Co y Mn 1-x-y O 2 ，0.7≤x≤1，0.0≤y≤0.3。
In an alternative embodiment, the mass ratio of the high nickel ternary material-fired material to the Zr-based UIO-66 is from 0.2 to 1.
In an alternative embodiment, the high nickel ternary material-fired material is mixed with the Zr-based UIO-66 at 500-900r/min for 30-60min.
In an alternative embodiment, the high temperature heat treatment is carried out at 450-700 ℃ for 2-8h;
the heating rate is 2-10 ℃/min.
In an alternative embodiment, the boron source comprises boric acid or boron oxide.
In an alternative embodiment, the mass ratio of boron source to primary cladding material is 0.3-1.
In an alternative embodiment, the primary coating material is mixed with the boron source at 500-900r/min for 30-60min.
In an alternative embodiment, the low temperature heat treatment is performed at 200-300 ℃ for 4-10h;
the heating rate is 2-10 ℃/min.
In a second aspect, the application also provides a high-nickel ternary cathode material, which is prepared by the preparation method.
In a third aspect, the application also provides a battery, and a preparation material of the battery comprises the high-nickel ternary cathode material.
The beneficial effect of this application includes:
the method has the advantages that through simple mechanical mixing and high-temperature heat treatment, zr-based UIO-66 is decomposed at high temperature to form a nano-particle coating layer with good dispersibility on the surface of the high-nickel ternary material calcined material in situ; further, the high-nickel ternary cathode material coated by the composite coating can be obtained by mixing the high-nickel ternary cathode material with boric acid and carrying out low-temperature heat treatment.
The high-nickel ternary cathode material has good cycle performance and rate performance, can prevent electrolyte permeation and surface interface side reaction, has a low charge transfer resistance value, and is beneficial to lithium ion transmission.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is an electron microscope scan of the high nickel ternary positive electrode materials of example 1, comparative example 2 and comparative example 3 in test example 1;
fig. 2 is an XRD pattern of the high nickel ternary positive electrode material of example 1 and the NCM-fired material as a blank comparison in experimental example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The high-nickel ternary cathode material provided by the present application, and the preparation method and battery thereof are specifically described below.
The application provides a preparation method of a high-nickel ternary cathode material, which comprises the following steps:
mixing a high-nickel ternary material primary-fired material (namely an NCM primary-fired material) with Zr-based UIO-66, and then carrying out high-temperature heat treatment in an oxygen atmosphere to obtain a primary coating material;
mixing the primary coating material with a boron source, and carrying out low-temperature heat treatment in an oxygen atmosphere to obtain a composite coated high-nickel ternary cathode material;
wherein the molecular formula of the high-nickel ternary material calcined material is LiNi x Co y Mn 1-x-y O 2 ，0.7≤x≤1，0.0≤y≤0.3。
By way of reference, the NCM fired material described above can be made in the following manner:
(1) preparing Ni by coprecipitation method x Co y Mn 1-x-y (OH) 2 Precursor (x is more than or equal to 0.7 and less than or equal to 1,0 and less than or equal to y is less than or equal to 0.3): the material NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 Weighing O according to a certain molar ratio (the molar ratio is x: y:1-x-y, the total amount of Ni, co and Mn is 0.2 mol/L), adding into deionized water, stirring at 400-750rpm to completely dissolve to obtain transition metal ion solution, pumping into a tank reactor, and adding into N 2 Stirring was continued under an atmosphere. Simultaneously, 0.2mol/L NaOH solution and a proper amount of NH are added 3 ·H 2 And O is mixed and then is input into the transition metal ion solution through a flow pump. The stirring speed was 700rpm, and pH =11.0 was maintained under control. The product is separated by vacuum filtration, washed by deionized water and dried in a vacuum oven at 120 ℃ to obtain Ni x Co y Mn 1-x-y (OH) 2 Precursors (e.g. Ni) 0.92 Co 0.05 Mn 0.03 (OH) 2 Precursor or Ni 0.85 Co 0.10 Mn 0.05 (OH) 2 Precursor).
(2) Ni to be obtained x Co y Mn 1-x-y (OH) 2 Precursor product and a proper amount of LiOH H 2 And (4) uniformly mixing the components. Placing the mixture in a box furnace, O 2 Heating up at a speed of 3 ℃/min in the atmosphere, firstly presintering for 6h at 550 ℃, then heating up to 750 ℃ at a speed of 3 ℃/min, calcining for 12h, naturally cooling to 120 ℃, and taking out to obtain LiNi x Co y Mn 1-x-y O 2 (NCM) positive electrode material (wherein, x is more than or equal to 0.7 and less than or equal to 1,0 and less than or equal to y is less than or equal to 0.3).
(3) Followed by LiNi x Co y Mn 1-x-y O 2 (NCM) the cathode material and distilled water are mixed and stirred (150-300 rpm) according to the proportion of 1.
It should be noted that other methods and conditions in the prior art can also be used to prepare the NCM calcined material, which is not described herein in detail.
By way of reference, the above-mentioned Zr-based UIO-66 can be prepared by:
weighing a small amount of zirconium chloride, adding the zirconium chloride into N, N-Dimethylformamide (DMF), and stirring to dissolve to obtain Zr 4+ An ionic solution. Dissolving a certain amount of 1,4-phthalic acid in DMF, stirring at the rotating speed of 350rpm for 1h, and dissolving to obtain a phthalic acid ligand solution. Adding Zr 4+ Pouring the ionic solution into a terephthalic acid solution, wherein the weight ratio of zirconium chloride: terephthalic acid: the mass ratio of DMF was 1. The well mixed solution was transferred to a 80mL Teflon lined autoclave and heated in an oven to 120 ℃ for 12-24h. After the autoclave was cooled to room temperature, the precipitate was collected by centrifugation with DMF solvent, followed by centrifugation and washing with DMF 3 times. Finally, the collected precipitate is freeze-driedDrying in a dryer for 36h to obtain Zr-based UIO-66.
It should be emphasized that, in the prior art, the MOF material generally used is Ni-MOF-74 or Co-MOF-74, that is, a related material containing metal cobalt or nickel, and specifically, the MOFs material doped with Zr, B and other elements is obtained first by a solution method; and mixing the doped MOFs material with a nickel-cobalt-manganese ternary positive electrode material, and carrying out secondary calcination in a nitrogen atmosphere to obtain the high-nickel ternary positive electrode material with the X (X = Zr, co, B) doped graphite carbon coating layer. However, in the above embodiment, after the high-temperature treatment in a nitrogen atmosphere in the presence of a reducing carbon material, trivalent Ni in the ternary material is caused 3+ The transformation to divalent nickel influences the capacity of the nickelic material.
The Zr-based UIO-66 used in the present application has a different channel structure from the MOF-74 described above, and ZrO obtained after the high-temperature treatment 2 Is an amphoteric metal substance and is favorable for resisting electrolyte LiPF 6 Small amount of corrosive substances (such as HF, PF) formed by decomposition 5 - ) Erosion of the anode material. And the secondary sintering of the coating adopts oxygen atmosphere, so that the high-valence Ni in the ternary cathode material can be maintained 3 + The ions exist, so that the excessive lithium-nickel mixed discharge caused by the formation of low-valence nickel is prevented, and the electrochemical performance of the NCM material is ensured.
The mass ratio of the high-nickel ternary material calcined material to the Zr-based UIO-66 is 100.
It should be noted that if the mass ratio of the high-nickel ternary material calcined material to the Zr-based UIO-66 is less than 100.2, the surface coating layer is easily too thin or incompletely coated, and the purpose of preventing the electrolyte from contacting the surface of the material is difficult to achieve; if the mass ratio of the high-nickel ternary material calcined material to the Zr-based UIO-66 is higher than 100.
Both the high nickel ternary material calcined material and the Zr-based UIO-66 can be blended in a high speed mixer. For reference, the mixing speed can be 500-900r/min (e.g., 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, 850r/min, 900r/min, etc.), and the mixing time can be 30-60min (e.g., 30min, 35min, 40min, 45min, 50min, 55min, 60min, etc.).
The high-temperature heat treatment (also understood as high-temperature sintering) can be carried out for 2-8h (such as 2h, 3h, 4h, 5h, 6h, 7h or 8 h) under the condition of 450-700 ℃ (such as 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃ or 700 ℃ and the like).
The temperature rise rate in the process can be 2-10 deg.C/min, such as 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min or 10 deg.C/min.
If the high-temperature heat treatment temperature is lower than 450 ℃ or the high-temperature heat treatment time is shorter than 2 hours, the ligand of Zr-UIO-66 is easy to cause incomplete terephthalic acid decomposition, and the organic ligand influences the ionic and electronic conductivity; if the high-temperature heat treatment temperature is higher than 700 ℃ or the high-temperature heat treatment time is longer than 10 hours, the nano-grade ZrO generated by the decomposition of the zirconium-based UIO-66 is easy to be caused 2 The network structure is agglomerated into large particles and a uniform thin layer coating on the surface cannot be achieved. If the temperature rise rate is slower than 2 ℃/min, the time consumption of the temperature rise process is easily overlong, the energy consumption is increased, and the target material is not easily obtained quickly; if the temperature rise rate is faster than 10 ℃/min, UIO-66 is easily and violently decomposed and converted into nano-grade ZrO 2 The particles are easy to agglomerate into large particles, even the particles directly fall off from the surface of the NCM, and ZrO is difficult to realize 2 The NCM material is uniformly adhered to the surface.
The high-temperature heat treatment can be carried out in a box furnace, and the pressure in the furnace is controlled to be 5-15Pa.
In the present application, the boron source may be boric acid or boron oxide.
The mass ratio of the boron source to the primary coating material may be 0.3 to 1, such as 0.3.
It should be noted that if the mass ratio of the boron source to the primary coating material is lower than0.3 2 Too little to be sufficient for ZrO 2 Coverage of network structure pores; if the mass ratio of the boron source to the primary cladding material is higher than 1 2 /ZrO 2 After the composite coating layer is coated, the lithium ion transmission and the final capacity and rate performance of the material are influenced.
The primary coating material and boron source described above can also be mixed in a high speed mixer.
Similarly, the mixing speed of the primary coating material and the boron source can be 500-900r/min (such as 500r/min, 550r/min, 600r/min, 650r/min, 700r/min, 750r/min, 800r/min, 850r/min or 900r/min, etc.), and the mixing time can be 30-60min (such as 30min, 35min, 40min, 45min, 50min, 55min or 60min, etc.).
Alternatively, the low temperature heat treatment (also understood as low temperature sintering) may be performed at 200-300 ℃ (e.g., 200 ℃, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, or 300 ℃, etc.) for 4-10h (e.g., 4h, 5h, 6h, 7h, 8h, 9h, or 10h, etc.).
The temperature rise rate in the process can also be 2-10 deg.C/min, such as 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, 5 deg.C/min, 6 deg.C/min, 7 deg.C/min, 8 deg.C/min, 9 deg.C/min or 10 deg.C/min.
In the application, the secondary coating of boric acid adopts solid-phase mixed coating, then the low-temperature heat treatment is carried out in an oxygen atmosphere, and the boric acid reacts with lithium salt at low temperature to form LiBO with high lithium ion conductivity 2 Is beneficial to improve Li + The transmission performance.
If the low-temperature heat treatment temperature is less than 200 ℃ or the low-temperature heat treatment time is less than 0.5h, boric acid and residual lithium are liable to not reach the reaction temperature and LiBO having lithium ion conductivity cannot be formed 2 (ii) a If the heat treatment temperature is higher than 300 ℃ or the heat treatment time at a low temperature is longer than 5 hours, liBO with poor conductivity is easily formed x Mixture of, influence Li + The transmission performance. Similarly, if the temperature rise rate is slower than 2 ℃/min, the time consumption of the temperature rise process is easy to be long, and the requirement of high efficiency and energy conservation is not met; if the temperature rise rate is faster than 10 ℃/min, the boron source is easily covered on the surfaceNon-uniformity, i.e. non-uniformity of the structure of the composite coating finally formed, i.e. final influence of Li + Uniformity of transmission at the interface.
The low-temperature heat treatment can also be carried out in a box furnace, the pressure in the furnace is controlled to be 5-10Pa, and the gas flow rate is controlled to be 2-5m 3 H is used as the reference value. And after low-temperature heat treatment, naturally cooling to 120-150 ℃.
On the basis, through simple mechanical mixing and high-temperature heat treatment, the Zr-based UIO-66 is decomposed at high temperature to form a nano-particle coating layer with better dispersibility on the surface of the high-nickel material in situ. Furthermore, the ternary cathode material coated by the composite coating is obtained by mixing the ternary cathode material with boric acid and performing low-temperature heat treatment, so that the phenomenon that a small amount of pore structures among nano oxide particles cause electrolyte to permeate and corrode the surface of the material can be avoided.
The advantages of the above method include:
(1) Reaction of boric acid with surface residual alkali to form LiBO 2 The content of residual alkali is reduced;
(2) The boric acid forms a molten state with fluidity after the temperature is 170 ℃ higher than the melting point, so that the pore structure of the nano particles can be filled, the obtained composite coating layer is compact, the surface interface of the material is better protected, and the side reaction of the surface interface is prevented;
（3）LiBO 2 the nano composite coating is a good lithium ion conductor, has thin thickness and small impedance, and is beneficial to improving the rate capability of the material.
In other words, the metal derived from the porous MOF serving as a precursor is oxidized into a porous nanostructure, so that the lithium ion shuttling is facilitated, the metal center of the MOF is surrounded and limited by ligands, and the metal is not easy to agglomerate, so that the derived ZrO is difficult to agglomerate 2 The particle size of the nano particles is small (20-50 nm) and the nano particles are distributed in a network structure, and meanwhile, through mechanical mixing, a coating layer formed by the MOF layer at the end of uniform distribution of NCM is uniform and thin; liBO with lithium ion conductivity constructed on nano oxide layer and at gap 2 The layer, on one hand, fills gaps among nano-oxide particles to form a compact coating layer, further prevents electrolyte permeation side reaction, improves circulation stability, and simultaneously improvesProvides a transmission channel of ions and is beneficial to improving the multiplying power performance.
In the prior art, zrO with larger grain size is directly prepared 2 When metal oxide (generally more than 50 nm) or MOF material and a sintering material are dry-mixed and sintered at high temperature for coating, the coating on the surface of the obtained material is in an island-shaped structure and is not compact enough, and the electrolyte can be contacted with the surface interface of the primary particle of NCM through a gap structure to generate side reaction, so that the structural stability is influenced; in addition, the coating components are mostly inactive, which is disadvantageous for Li + Transmission, resulting in reduced rate performance.
Correspondingly, the application also provides a high-nickel ternary cathode material which is prepared by the preparation method.
The high-nickel ternary cathode material is UIO-66/H 3 BO 3 The surface of the composite coated NCM sample is uniformly distributed with fluffy flocculent ZrO formed by UIO-66 pyrolysis 2 A nanoparticle; and LiBO formed by reaction of boric acid and residual lithium on the surface 2 The surface of the primary particles and gaps among the particles are uniformly distributed, and the whole secondary ball is compact. The coated sample still keeps the good layered structure of the ternary cathode material, and the coating layer is thin, so that no new phase or mixed phase is generated.
In addition, the composite coated sample shows excellent performance in specific discharge capacity at 0.1C rate and charge-discharge cycle stability at 1C rate. The boric acid is in a molten state and is filled with ZrO during high-temperature treatment 2 Gaps between the nanoparticles and the primary particles of the NCM, allowing the NCM to contact the surface-coated porous ZrO 2 The contact of the nano particles is more compact, and the contact resistance between the nano particles and the nano particles is greatly reduced. UIO-66 derived porous ZrO 2 Nanoparticles and LiBO 2 The composite coating on the surface of the NCM primary particles forms ZrO which is more independent than ZrO 2 The more compact protective layer can obstruct the corrosion of the electrolyte and inhibit the surface interface side reaction. The sample coated with the composite material has higher initial coulombic efficiency, which indicates that an electrolyte interface film formed in initial charge and discharge is thinner, side reactions are less, and consumed lithium ions are less, so that higher discharge capacity is ensured. In addition, the composite coated samples showed comparable to singleSolely ZrO 2 Lower charge transfer resistance values of the cladding, which is mainly due to LiBO formed on the surface 2 Is beneficial to lithium ion conduction.
In addition, the application also provides a battery, and the preparation material of the battery comprises the high-nickel ternary cathode material.
For example, the obtained high-nickel ternary cathode material, a conductive agent and a binder PVDF are mixed according to a ratio of 8.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a high-nickel ternary cathode material, which is prepared by the following method:
step (1), blending with Zr-based UIO-66, and sintering:
the NCM-fired material was blended with the Zr-based UIO-66 in a mass ratio of 100.5 in a high-speed mixer at a rotation speed of 600r/min for 45min, and then the mixture was contained in a sagger and transferred into a box furnace. In an oxygen atmosphere (the pressure in the furnace is controlled at 10Pa, and the gas flow is 4m 3 And h) heating to 500 ℃ at the speed of 3 ℃/min, sintering for 8h, and then naturally cooling to 120 ℃ and taking out to obtain the primary coating material Zr-NCM.
And (2) blending and sintering Zr-NCM and boric acid:
reacting the above Zr-NCM with H 3 BO 3 Mixing the materials in a high-speed mixer at a mass ratio of 100:0.5 at a rotating speed of 600r/min for 45min, and then placing the mixture in an oxygen atmosphere (gas flow is 4 m) in a box furnace 3 And h) (the pressure in the furnace is controlled to be 10 Pa), the temperature is increased to 250 ℃ at the speed of 5 ℃/min, the mixture is sintered for 10h, and the mixture is taken out after being naturally cooled to 120 ℃, and the mixture is marked as a secondary coating material Zr/B-NCM-1 (namely the high-nickel ternary cathode material).
The NCM calcined material is prepared by the following steps:
(1) preparing Ni by coprecipitation method 0.92 Co 0.05 Mn 0.03 (OH) 2 Precursor: the material NiSO 4 ·6H 2 O、CoSO 4 ·7H 2 O and MnSO 4 ·H 2 Weighing O according to a certain molar ratio (the molar ratio is x: y:1-x-y, the total amount of Ni, co and Mn is 0.2 mol/L), adding into deionized water, stirring at 600rpm to completely dissolve to obtain transition metal ion solution, pumping into a tank reactor, and adding N 2 Stirring was continued under an atmosphere. Simultaneously, 0.2mol/L NaOH solution and a proper amount of NH are added 3 ·H 2 And O is mixed and then is input into the transition metal ion solution through a flow pump. The stirring speed was 700rpm, and pH =11.0 was maintained under control. The product was vacuum filtered and separated, washed with deionized water and dried in a vacuum oven at 120 ℃.
(2) Ni to be obtained 0.92 Co 0.05 Mn 0.03 (OH) 2 Precursor product and LiOH H 2 And O is uniformly mixed, wherein the mass ratio of Ni + Co + Mn metal ions to lithium salt is ensured to be 1. Placing the mixture in a box furnace, O 2 Heating up at a speed of 3 ℃/min in the atmosphere, firstly presintering for 6h at 550 ℃, then heating up to 750 ℃ at a speed of 3 ℃/min, calcining for 12h, naturally cooling to 120 ℃, and taking out to obtain LiNi 0.92 Co 0.05 Mn 0.03 O 2 (NCM) positive electrode material.
(3) Followed by LiNi 0.92 Co 0.05 Mn 0.03 O 2 (NCM) the cathode material and distilled water were mixed and stirred (200 rpm) at a ratio of 1.
The above Zr-based UIO-66 was prepared in the following manner:
zr was obtained by weighing 0.106g of zirconium chloride and adding to 25mLN, N-Dimethylformamide (DMF), and dissolving by stirring at 350rpm for about 0.5h 4+ An ionic solution. Subsequently, 0.068g1, 4-phthalic acid was added to 25mL of DMF and dissolved by stirring at 350rpm for 1 hour to obtain a phthalic acid ligand solution. Zr (B) is added 4+ Ionic solutionsPoured into the terephthalic acid solution and stirred continuously (350 rpm) for 1h. The uniformly mixed solution was transferred to an 80mL teflon lined autoclave and heated to 120 ℃ in an oven for 12h. After the autoclave was cooled to room temperature, the precipitate was collected by centrifugation with DMF solvent, followed by centrifugation and washing with DMF 3 times. Finally, the collected precipitate was dried in a freeze dryer for 36 hours to obtain Zr-based UIO-66.
Example 2
This example differs from example 1 in that:
Zr-NCM and H 3 BO 3 The mass ratio of (1) is 100.
The other conditions were the same.
The obtained secondary coating material is referred to as Zr/B-NCM-2 (namely, high-nickel ternary cathode material).
Best mode for carrying out the invention
This example differs from example 1 in that:
the mass ratio of the NCM calcined material to the Zr-based UIO-66 was 100.2;
the high-temperature heat treatment temperature is 700 ℃.
The other conditions were the same.
The obtained secondary coating material is referred to as Zr/B-NCM3 (i.e. high nickel ternary cathode material).
Example 4
This example differs from example 1 in that:
the high-temperature heat treatment is sintering at 700 ℃ for 8h.
Zr-NCM and H 3 BO 3 The mass ratio of (A) to (B) is 100.
The low-temperature heat treatment temperature is 300 ℃.
The other conditions were the same.
The obtained secondary coating material is referred to as Zr/B-NCM-4 (namely a high-nickel ternary cathode material).
Example 5
The difference between this example and example 1 is: the precursor of the NCM one-step sintered material is Ni 0.85 Co 0.10 Mn 0.05 (OH) 2 。
Comparative example 1
The comparative example differs from example 1 in that:
the NCM calcined material is coated by nano zirconium dioxide instead of Zr-based UIO-66, and the NCM calcined material is coated by nano zirconium dioxide and boric acid at the same time.
The method comprises the following specific steps:
the NCM calcined material, nano zirconium dioxide (particle size about 50 nm) and boric acid were blended in a high-speed mixer at a rotation speed of 600r/min for 45min, and directly sintered at 500 ℃ for 8h to obtain a control sample 1.
The mass ratio of the NCM calcined material to the nano zirconium dioxide to the boric acid is 100.5.
Comparative example 2
This comparative example differs from example 1 in that:
there is no step (2), which is a primary coating material Zr-NCM coated with only Zr-based UIO-66.
Comparative example 3
This comparative example differs from example 1 in that:
carrying out hydrothermal reaction on the UIO-66 and NCM calcined material according to the mass ratio of 0.5 3 BO 3 Mixed and sintered for 10 hours at 250 ℃.
That is, the UIO-66 and NCM calcined materials were coated in a different manner from that of example 1.
Comparative example 4
This comparative example differs from example 1 in that:
UIO-66: boric acid: the mass ratio of the NCM calcined material is 0.5:0.5:100, and the three are directly and simultaneously mixed and then sintered for 8 hours at 500 ℃.
That is, no secondary coating is used and no low temperature sintering step is used.
Comparative example 5
This comparative example differs from example 1 in that:
UIO-66: boric acid: the mass ratio of the NCM calcined material is 0.5:0.5:100, and the three are directly and simultaneously mixed and then sintered for 10 hours at 250 ℃.
That is, no secondary coating is used and no high temperature sintering step is used.
Test example 1
(1) The results of electron microscope scanning of the high nickel ternary positive electrode materials obtained in example 1 and comparative examples 2 and 3 are shown in fig. 1.
FIGS. 1 (a) and (b) are SEM images of the high-nickel ternary positive electrode material obtained after coating with UIO-66 mixed with boric acid in example 1, and the latter is an enlarged view of the former; (c) And (d) SEM of Zr-NCM which is a primary coating material coated only with UIO-66 in comparative example 2, the latter being an enlarged view of the former; (e) And (f) SEM of the high nickel ternary positive electrode material formed by the hydrothermal reaction of comparative example 3, the latter being an enlarged view of the former.
As can be seen from fig. 1: all the materials have no obvious change in the size of the secondary spheres after coating, and the coated nano particles are distributed on the surface of the primary particles. Example 1 corresponding UIO-66/H 3 BO 3 The surface of the composite coated high-nickel ternary cathode material is uniformly distributed with fluffy flocculent ZrO formed by UIO-66 pyrolysis 2 Nanoparticles simultaneously with UIO-66-derived ZrO alone in comparative example 2 2 In contrast to the coated samples, liBO formed due to the reaction of boric acid with surface residual lithium 2 The surface of the primary particles and gaps among the particles are uniformly distributed, and the whole secondary ball looks more compact; in comparative example 3, zrO obtained by coating UIO-66 on the NCM surface in situ through the hydrothermal reaction process and then performing heat treatment 2 Coated samples in which the secondary spheres had more fragmentation, possibly causing less sphere breakage upon hydrothermal reaction agitation at UIO-66, and in addition, zrO having UIO-66 derived on the surface thereof was observed 2 The nanoparticles coat the particles, but the particles are not uniform in size, and may be affected by non-uniform residual alkali on the surface of the NCM due to the UIO growth process.
(2) Fig. 2 is an XRD pattern of the composite coated high nickel ternary positive electrode material obtained in example 1, which is compared with a blank of NCM calcined material without any coating. Wherein (a) is the whole XRD pattern, and (b) is the enlarged view of part of diffraction peak area.
As shown in fig. 2, the diffraction position of the coated sample is consistent with that of the uncoated sample, and meanwhile, the (018)/(110) crystal plane diffraction peak is obviously split, which indicates that the coated sample still maintains a good layered structure of the ternary cathode material; the absence of new diffraction peaks indicates that the cladding is very thin and does not lead to the formation of new phases or hetero-phases.
Test example 2
The high-nickel ternary positive electrode materials obtained in the examples 1-5 and the comparative examples 1-5 are respectively mixed with a conductive agent and a binder PVDF according to the proportion of 8.
The obtained button cell was subjected to the following performance tests, and the results are shown in table 1.
TABLE 1 comparison of the Properties of the materials of the different examples and comparative examples
| Characterization of the sample | 0.1C discharge capacity Quantity (mAh/g) | First coulomb Efficiency (%) | 1C discharge capacity Quantity (mAh/g) | * Capacity protection Retention (%) | R ct (Ω) | |
| Example 1 | Zr-NCM and H 3 BO 3 According to the mass ratio of 100:0.5, N CM:Zr=100 : 0.5 | 219 | 90.16 | 199.5 | 9 1 .6 | 26 |
| example 2 | Zr-NCM and H 3 BO 3 In a mass ratio of 100:1 | 218.5 | 89.5 | 200.4 | 90.6 | 48 |
| Example 3 | The mass ratio of the NCM calcined material to the Zr-based UIO-66 is 100: 0.2 (ii) a The high-temperature heat treatment temperature is 700 DEG C | 221 | 91 | 203.2 | 91.4 | 21.1 |
| Example 4 | Zr-NCM and H 3 BO 3 The mass ratio of (A) to (B) is 100: 0.3; high temperature The heat treatment temperature is 700 ℃; the low-temperature heat treatment temperature is 300 DEG C | 218 | 89.5 | 200.3 | 91.07 | 58 |
| Example 5 | Li Ni 0.8 5 Co 0. 10 Mn 0.0 5 O 2 | 2 01 | 89 | 1 81 | 9 6.2 | 39.7 |
| Comparative example 1 | Z rO 2 The boric acid one-step high-temperature sintering capacity is lower | 207.1 | 87.1 | 193 | 89.2 | 88 |
| Comparative example 2 | Zr coating, no boric acid coating (poor stability) | 21 5.6 | 88.7 | 197.4 | 87.9 | 95 |
| Comparative example 3 | Hydrothermal reaction | 165 | 81.2 | 136.1 | 89.6 | 85 |
| Comparative example 4 | Does not adopt a secondary coating form and does not have a low-temperature sintering step | 212.6 | 88 . 6 | 195.7 | 86.7 | 96.1 |
| Comparative example 5 | A secondary coating form is not adopted and a high-temperature sintering step is not adopted; sintering, capacity, The multiplying power is lower | 21 2 .9 | 89. 0 | 197. 5 | 8 8 .7 | 93 |
* After the charge-discharge activation at 0.1C for one turn, the charge-discharge cycle is carried out at 1C rate.
As can be seen from Table 1, the specific discharge capacity (mAh/g) at 0.1C rate and the charge-discharge cycle stability at 1C rate of the composite coated sample are both more excellent, and the boric acid is in a molten state and filled with ZrO during high-temperature treatment 2 Gaps between the nanoparticles and the primary particles of the NCM, allowing the NCM to contact the surface-coated porous ZrO 2 The contact of the nano particles is more compact, and the contact resistance between the nano particles and the nano particles is greatly reduced. UIO-66 derived porous ZrO 2 Nanoparticles and LiBO 2 The composite coating on the surface of the NCM primary particles forms ZrO which is more independent than ZrO 2 A more compact protective layer, the corrosion of the blocked electrolyte and the surface interface side reaction. The higher first coulombic efficiency also indicates that the electrolyte interface film formed in the first charge and discharge is thinner, the side reaction is less, the consumed lithium ions are less, and thus the higher discharge capacity is ensured. The sample after the simultaneous composite coating shows ZrO better than that of the ZrO alone 2 Lower charge transfer resistance values of the cladding due to surface-formed LiBO 2 Is beneficial to lithium ion conduction.
In addition, it is worth pointing out that the sample obtained in comparative example 3 shows significantly lower specific capacity and poorer cycling stability, which is mainly because when the coating layer of UIO-66 grows in situ on the NCM surface, because the NCM reacts with the lithium ions in the NCM for a long time at high temperature in solvents such as water and the like, the lithium ions are easy to dissolve out, and the subsequent procedures such as water washing and the like are involved, the dissolved lithium ions are taken away in a large amount in the water washing process, so that the surface of the NMC positive electrode material and even the bulk structure are poor in lithium. The porous metal-coated NCM material obtained by high-temperature calcination seriously affects the subsequent charge and discharge capacity and cycle performance due to extremely poor lithium.
In summary, the method provided by the application can be used for preparing the high-nickel ternary cathode material with better cycle performance and rate performance, and the corresponding material can prevent electrolyte permeation and surface interface side reaction, has a lower charge transfer resistance value and is beneficial to lithium ion transmission.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the high-nickel ternary cathode material is characterized by comprising the following steps of:
mixing a high-nickel ternary material primary-fired material with Zr-based UIO-66, and then carrying out high-temperature heat treatment in an oxygen atmosphere to obtain a primary coating material;
mixing the primary coating material with a boron source, and carrying out low-temperature heat treatment in an oxygen atmosphere to obtain a composite coated high-nickel ternary cathode material;
wherein the molecular formula of the high-nickel ternary material calcined material is LiNi x Co y Mn 1-x-y O 2 ，0.7≤x≤1，0.0≤y≤0.3。
2. The method according to claim 1, wherein the mass ratio of the high-nickel ternary material-fired material to the Zr-based UIO-66 is from 100.2 to 1.
3. The method of claim 1, wherein the high nickel ternary material calcined material is mixed with the Zr-based UIO-66 at 500-900r/min for 30-60min.
4. The method according to claim 1, wherein the high temperature heat treatment is performed at 450 to 700 ℃ for 2 to 8 hours;
the heating rate is 2-10 ℃/min.
5. The method of claim 1, wherein the boron source comprises boric acid or boron oxide.
6. The production method according to claim 5, wherein the mass ratio of the boron source to the primary coating material is 0.3 to 1.
7. The preparation method according to claim 6, wherein the primary coating material and the boron source are mixed for 30-60min under the condition of 500-900 r/min.
8. The method according to claim 1, wherein the low temperature heat treatment is performed at 200 to 300 ℃ for 4 to 10 hours;
the heating rate is 2-10 ℃/min.
9. A high-nickel ternary cathode material, which is prepared by the preparation method of any one of claims 1 to 8.
10. A battery prepared from a material comprising the high-nickel ternary positive electrode material of claim 9.
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